Saccharinic acids four-carbon

Compton, Jack, The Molecular Constitution of Cellulose, III, 185-228 Conchie, J., Levvy, G. A., and Marsh, C. A., Methyl and Phenyl Glycosides of the Common Sugars, XII, 157-187 Crum, James D., The Four-carbon Saccharinic Acids, XIII, 169-188... 

Sacchari Ocation, of wood, 4, 153-188 Saccharinic acids, 12, 35-79 four-carbon, 13, 169-188 Schardinger dextrins, 12, 189-260... 

III. Tables of Properties of the Four-Carbon Saccharinic Acids and their Derivatives. 187... 

The saccharinic acids formed from some of the pentoses and hexoses have been the objects of study by Nef and his students. Glattfeld and Hanke reported in 1918 that, during the oxidation of maltose in alkaline solution, an acid had been produced whose phenylhydrazide had an analysis agreeing perfectly with that calculated for a four-carbon saccharinic acid. Furthermore, the properties of the free aeid were those which would be expected of one of these acids. Its configuration could not, however, be reported at that time because of the absence of data as to the properties and constants of the four-carbon saccharinic acids. Nef had also referred to the handicap which this lack of information had imposed on the work with sugars in alkaline solution. Consequently, with this in mind, Glattfeld began in 1920 the systematic synthesis of the four-carbon saccharinic acids. 

II. Synthesis of the Four-Carbon Saccharinic Acids 1. 3,4-Dihydroxybutanoic Adds... 

Dihydroxybutanoic acid, a 3-deoxytetronic acid, is the only theoretically possible four-carbon metasaccharinic acid it was isolated by Nef in the dl form (Ilab) in the course of his work on the action of sodium hydroxide on D-arabinose. It therefore constitutes the only four-carbon saccharinic acid isolated to date from a sugar-alkali reaction. Resolution of this on acid (Ilab) was accomplished by Nef, who showed that the dextrorotatory acid (Ila) upon oxidation gave rise to 2-deoxy-L-f/Z2/cero-tetraric acid [(-)-)-d-malic acid XV]. During the course of this work, several derivatives of the L and DL saccharinic acids (lib and Ilab) were prepared, but only the brucine salt of the d acid (Ila) was reported. 

Of the five positional isomers of the four-carbon saccharinic acids theoretically possible, 3-hydroxy-2-(hydroxymethyl)propanoic acid (VI) is the only one that lacks an asymmetric carbon atom and is optically inactive and unresolvable. The first attempt at its synthesis, by Glattfeld and cowork-ers, " was by a direct method. The reaction of 2-chloro-2-deoxyglyceritol (LII) [prepared from allyl alcohol (LI) by reaction with hypochlorous acid] with cyanide ion and subsequent hydrolysis of the anticipated nitrile (LIII) should have produced the desired 3-hydroxy-2-(hydroxymethyl)-... 

The following Tables give the melting points and optical rotations of the four-carbon saccharinic acids and their derivatives thus far prepared. 

D-Erythro-pentulose 1,5-diphosphate (20) with alkali gives the saccharinic acid monophosphate (21), a process suggested to parallel that occurring during the incorporation of pentose chains into the base unit of riboflavin. It was proposed that decarboxylation of a compound such as (21) provides the four carbon atoms... 

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